JPH0646297B2 - Color image forming method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically, it has excellent color reproducibility and color image fastness, and The present invention relates to a method for forming a color image from a silver halide color photographic light-sensitive material, in which processing fluctuations, that is, gradation fluctuations due to fluctuations in processing liquid composition, processing time, processing temperature, etc.

(Prior Art) A silver halide color photographic light-sensitive material is exposed to light and developed to give a desired image as is well known, but it reacts with a photosensitive silver halide emulsion and an oxidized product of an aromatic primary amine developing agent. A method using a so-called dye-forming coupler (hereinafter simply referred to as a coupler) that forms a dye by using a dye is often used. Among them, a combination of a yellow coupler, a cyan coupler and a magenta coupler is usually used for a color photographic light-sensitive material.

Of these, 5 has been frequently used as a magenta coupler.
The magenta dye obtained from the pyrazolone coupler is 4
There are major problems in color reproduction, such as having secondary absorption near 30 nm and poor bottoming on the long wave side.

Therefore, pyrazoloazole couplers have been developed in order to improve these drawbacks. The magenta dye obtained by coupling this coupler with the oxidation product of the aromatic primary amine developing agent does not have a side absorption at around 430 nm in an ethyl acetate solution, and has a high-purity magenta with good absorption tail on the long wave side. It has the characteristic of exhibiting color. Furthermore, the light fastness of the color image thus obtained is good.

On the other hand, a silver halide color photographic light-sensitive material is required to provide a stable color image under varying developing conditions as an important characteristic. For example, as the development processing conditions, the composition of the developing solution in the processing step varies depending on various factors such as the history of continuous processing, that is, the amount of the processed photosensitive material, the amount of replenishment of the solution, and the structure of the processor (so-called running solution). According to the research conducted by the present inventors, it has been found that the stability of a color image with respect to this process variation can be evaluated by the magnitude of the change in the sensitometric curve with the lapse of color development time.

(Problems to be Solved by the Invention) The inventors of the present invention have made various studies on the stability of color images of silver halide color photographic light-sensitive materials with respect to the processing fluctuation of the above continuous processing time. When a coupler and a silver halide grain are combined and processed with a developer containing an aromatic primary amine as a main agent, the sensitivity change of the sensitometry curve with the lapse of color development time is a 5-pyrazolone type coupler. It was found that the sensitivity was smaller than the sensitivity change of the sensitometry curve obtained by combining the same processing with the above and the same treatment. However, with the increasing demand for color photography, there is a growing demand for simplification and speeding up of processing of color photosensitive materials.
It cannot be said that the stability of a color image and the suitability for rapid processing of a silver halide color photographic light-sensitive material using this pyrazoloazole-based coupler with respect to processing variations are still satisfactory.

Therefore, the object of the present invention is to reduce the sensitivity change of the sensitometry curve with the lapse of color development time during continuous processing with a developer containing an aromatic primary amine as a main component,
Another object of the present invention is to provide a silver halide light-sensitive material having a small change in gradation.

(Means for Solving the Problems) The inventors of the present invention have conducted extensive studies to develop a silver halide color photographic light-sensitive material satisfying such demands, and as a result, pyrazoloazole-based couplers and silver halide grains have been obtained. And a processing solution containing an aromatic primary amine as the main agent, the crystals of silver halide emulsion grains are sensitive to the sensitivity change and gradation change of the sensitometry curve with the lapse of color development time. The influence of the shape, especially as silver halide, use silver halide grains of a specific normal crystal instead of the conventional general abnormal crystal, and combine with a specific pyrazoloazole coupler to replenish the color developer. It has been found that the continuous development below can remarkably reduce the sensitivity change and gradation change of the sensitometry curve with the lapse of color development time. The present invention has been accomplished based on this finding.

That is, the present invention relates to a pyrazoloazole coupler and the following formula (I) AgCl _x Br _y I _1-xy (I) (wherein 0 ≦ x ≦ 1, 0 ≦ y ≦ 10 ≦ 1−x−y ≦ 0.02), and a silver halide color photographic light-sensitive material having a silver halide grain composed of a normal crystal having a twin content of 5% or less.

The preferred embodiments of the present invention will be described below.

The normal crystal of the silver halide grain used in the present invention means a regular hexahedron in which the outer shape of the grain is surrounded by {100} planes, {1
The rhombodecahedron surrounded by the 10} plane, the regular octahedron surrounded by the {111} plane, and the tetrahedron surrounded by the {100} plane and the {111} plane.

The specific method for measuring the twin content in the present invention is as follows.

The silver halide grains of the emulsion of the present invention are photographed by the replica method. For 600 or more silver halide grains, normal crystals and twin crystals are classified according to the form of the silver halide grains, and the twin crystal content is calculated by the following formula.

Regarding the twin morphology classification, for example, E. Klein,
H. J. Mets and E. Moiser's "Photographische Correspondents" (Photographische Korr
espondenz) Volume 99 (published in 1963) on page 99 and subsequent pages, and Volume 100 (published in 1964) on page 57 and subsequent pages can be referred to.

The variation coefficient of grain size of the silver halide grains is preferably 25% or less, more preferably 20% or less. Here, the particle size means the diameter of a circle having the same area as the projected area of an electron micrograph of a particle, and the coefficient of variation is
It shall be defined in the following.

Now, the _one thing _n having a particle size _{d 1,} the _{two n} those of _{d 2,} is _{n i} number ones ... _{d i} Assuming there is, The coefficient of variation is defined as S / × 100%.

If the coefficient of variation exceeds 25%, the sensitivity change and gradation change of the sensitometry curve with the passage of the color development time increase, which is not preferable.

The twin content is 5% or less (the value examined for the number of particles of 277 or more), but it is desirable to be as small as possible. If the twin content exceeds 5%, the sensitivity change and gradation change of the sensitometry curve with the lapse of color development time increase, which is not preferable.

The average particle size is preferably 0.2 to 0.9 μm, particularly preferably 0.3 to 0.7 μm.
This average particle size is 277 according to an electron micrograph.
It is a value obtained by measuring more than one particle. When the average particle size is less than 0.2 μm, the effect of gradation variation with the lapse of color development time is generally small. On the other hand, when the particle size exceeds 0.9 μm, the size of the grains is large, so that the progress of development is controlled by the size of the silver halide grains, and the effect of the present invention is not generally apparent. Preparation of a silver halide emulsion having a controlled grain size distribution and crystal form as described above is achieved by forming silver halide grains in the presence of a silver halide solvent.

As the silver halide solvent, in addition to inorganic compounds such as ammonia and thiocyanate, organic compounds such as thioethers, amines and thioureas are known, and any of these is effective, The following general formula (X)
By using a compound of thiourea as shown in
A silver halide emulsion having a regular crystal form and a nearly uniform grain size distribution can be obtained.

General formula (X) (In the formula, R _{7 to} R ₁₀ may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms. R ₈ and R ₁₀ are linked to each other to form a 5- or 6-membered ring. May be formed.

<Example of compound> (1) (2) (3) (4) (5) (6) These compounds are used in a proportion of 5 × 10 ⁻³ mol to 5 × 10 ⁻⁶ mol with respect to 1 mol of silver halide whose precipitation has been completed.
It is desirable to allow it to exist during grain formation.

Examples of the pyrazoloazole-based coupler used in the present invention include those represented by the following general formula (II).

General formula (In the formula, R ₁ represents a hydrogen atom or a substituent, X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developer, Za, Zb and Zc represent methine, It represents a substituted methine, = N- or -NH-, and one of the Za-Zb bond and the Zb-Zc bond is a double bond and the other is a single bond.The aromatic ring is fused at Zb-Zc. It may also be included.) Also includes a case where R ₁ or X forms a dimer or higher multimer. Further, when Za, Zb or Zc is a substituted methine, the case where the substituted methine forms a dimer or higher multimer is also included.

Hereinafter, the pyrazoloazole compound used in the present invention will be described in more detail.

In the general formula (II), the multimer means a compound having two or more groups represented by the general formula (II) in one molecule, and a bis compound and a polymer coupler are also included therein. Here, the polymer coupler may be a homopolymer consisting only of a monomer having a portion represented by the general formula (II) (preferably having a vinyl group, hereinafter referred to as vinyl monomer), or an aromatic primary amine. A copolymer may be prepared with a non-color-forming, ethylene-like monomer that does not couple with the oxidized developer.

Among the pyrazoloazole-based magenta couplers represented by the general formula (II), preferred are those represented by the following general formula (II
I), (IV), (V), (VI), (VII), (VIII), and (IX).

Among the couplers represented by the general formulas (III) to (IX),
Preferred for the purposes of the present invention are the general formulas (III) and (VI)
And (VII), more preferred are those represented by the general formula (V
II).

In the general formulas (III) to (IX), R ¹¹ , R ¹² and R
¹³ may be the same as or different from each other, respectively, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, a silyloxy group. Group, sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group,
Represents a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and X represents a hydrogen atom, a halogen atom, a carboxy group or an oxygen atom, a nitrogen atom or a sulfur atom. A group which is coupled to the carbon at the coupling position via the coupling-off group. R ¹¹ , R ¹² , R ¹³ or X may be a divalent group to form a bis form.

Further, it may be in the form of a polymer coupler in which the coupler residue represented by the general formulas (III) to (IX) exists in the main chain or side chain of the polymer, and it is particularly derived from a vinyl monomer having a moiety represented by the general formula. Polymers are preferred in which R ¹¹ , R ¹² , R ¹³ or X represents a vinyl group or a linking group.

More specifically, R ¹¹ , R ¹² and R ¹³ are each a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.),
Alkyl group (eg, methyl group, propyl group, t-butyl group, trifluoromethyl group, tridecyl group, 3-
(2,4-di-t-amylphenoxy) propyl group, allyl group, 2-dodecyloxyethyl group, 3-phenoxypropyl group, 2-hexylsulfonyl-ethyl group, cyclopentyl group, benzyl group, etc., aryl group ( For example,
Phenyl group, 4-t-butylphenyl group, 2,4-di-
t-amylphenyl group, 4-tetradecanamidophenyl group, etc.), heterocyclic group (eg, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.), cyano group, alkoxy group (eg, , Methoxy group, ethoxy group, 2-methoxyethoxy group, 2-dodecyloxyethoxy group, 2-methanesulfonylethoxy group, etc.), aryloxy group (eg, phenoxy group, 2-
Methylphenoxy group, 4-t-butylphenoxy group etc.), heterocyclic oxy group (eg 2-benzimidazolyloxy group etc.), acyloxy group (eg acetoxy group, hexadecanoyloxy group etc.), carbamoyloxy group ( For example, an N-phenylcarbamoyloxy group,
N-ethylcarbamoyloxy group etc.), silyloxy group (eg trimethylsilyloxy group etc.), sulfonyloxy group (eg dodecylsulfonyloxy group etc.),
Acylamino group (for example, acetamide group, benzamide group, tetradecanamide group, α- (2,4-di-t-
Amylphenoxy) butyramide group,-(3-t-butyl-4-hydroxyphenoxy) butyramide group, α
-{4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide group, etc.), anilino group (eg, phenylamino group, 2-chloroanilino group, 2-chloro-5
-Tetradecanamido anilino group, 2-chloro-5-dodecyloxycarbonylanilino group, N-acetylanilino group, 2-chloro-5- {α- (3-t-butyl-4-
Hydroxyphenoxy) dodecanamido} anilino group, etc.), ureido group (eg, phenylureido group, methylureido group, N, N-dibutylureido group, etc.), imide group (eg, N-succinimide group, 3-benzylhydantoinyl) Group, 4- (2-ethylhexanoylamino) phthalimide group, etc., sulfamoylamino group (for example, N, N-dipropylsulfamoylamino group, N
-Methyl-N-decylsulfamoylamino group, etc.), alkylthio group (for example, methylthio group, octylthio group, tetradecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3- (4-t -Butylphenoxy) propylthio group, etc.), an arylthio group (for example, phenylthio group, 2-butoxy-5-t-octylphenylthio group, 3-pentadecylphenylthio group, 2-carboxyphenylthio group, 4-tetradecaneamidophenyl) Thio group), heterocyclic thio group (for example,
2-benzothiazolylthio group etc.), alkoxycarbonylamino group (eg methoxycarbonylamino group, tetradecyloxycarbonylamino group etc.), aryloxycarbonylamino group (eg phenoxycarbonylamino group, 2,4-di- tert-butylphenoxycarbonylamino group, etc.), sulfonamide group (eg,
Methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecanesulfonamide group, 2-methyloxy-5-t-butylbenzenesulfonamide group, etc.), carbamoyl group (for example, N-ethylcarbamoyl group, N, N-dibutylcarbamoyl group, N- (2-dodecyloxyethyl) carbamoyl group, N-methyl-N
-Dodecylcarbamoyl group, N- {3- (2,4-di-
tert-amylphenoxy) propyl} carbamoyl group, etc.), acyl group (eg, acetyl group, (2,4-di-tert-amylphenoxy) acetyl group, benzoyl group, etc.), sulfamoyl group (eg, N-ethylsulfa group) Moyl group, N, N-dipropylsulfamoyl group,
N- (2-dodecyloxyethyl) sulfamoyl group,
N-ethyl-N-dodecylsulfamoyl group, N, N-
Diethylsulfamoyl group, etc.), sulfonyl group (eg, methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), sulfinyl group (eg, octansulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, etc.), Represents an alkoxycarbonyl group (eg, methoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, 3-pentadecyloxy-carbonyl group, etc.), X is a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, etc.), a carboxy group, or a group linked by an oxygen atom (for example, an acetoxy group, a propanoyloxy group, a benzoyloxy group, , 4-dichlorobenzoyloxy group, ethoxooxaloyloxy group, pyrvinyloxy group, cinnamoyloxy group, phenoxy group, 4-cyanophenoxyl group, 4-methanesulfonamidophenoxy group, 4-methanesulfonylphenoxy group, α-naphthoxy group, 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzyloxy group, 2-phenethyloxy group, 2-
Phenoxyethoxy group, 5-phenyltetrazolyloxy group, 2-benzothiazolyloxy group, etc.), groups linked by nitrogen atoms (for example, benzenesulfonamide group, N-
Ethyltoluenesulfonamide group, peptafluorobutanamide group, 2,3,4,5,6-pentafluorobenzamide group, octanesulfonamide group, p-cyanophenylureido group, N, N-diethylsulfamoylamino group , 1-piperidyl group, 5,5-dimethyl-2,4
-Dioxo-3-oxazolidinyl group, 1-benzyl-
Ethoxy-3-hydantoinyl group, 2N-1,1-dioxo-3 (2H) -oxo-1,2-benzisothiazolyl group, 2-oxo-1,2-dihydro-1-pyridinyl group, imidazolyl group, Pyrazolyl group, 3,5-diethyl-1,2,4-triazol-1-yl, 5- or 6-bromo-benzotriazol-1-yl, 5-methyl-1,2,3,4-triazole-1 -Yl group, benzimidazolyl group, 3-benzyl-1-hydantoinyl group, 1-benzyl-5-hexadecyloxy-3-hydantoinyl group, 5-methyl-1-tetrazolyl group, etc.),
Arylazo group (for example, 4-methoxyphenylazo group, 4-pivaloylaminophenylazo group, 2-naphthylazo group, 3-methyl-4-hydroxyphenylazo group, etc.), group linked by sulfur atom (for example, phenylthio Group, 2-carboxyphenylthio group, 2-methoxy-5
-T-octylphenylthio group, 4-methanesulfonylphenylthio group, 4-octanesulfonamidophenylthio group, 2-butoxyphenylthio group, 2- (2-hexanesulfonylethyl) -5-tert-octylphenylthio group , Benzylthio group, 2-cyanoethylthio group, 1-ethoxycarbonyltridecylthio group, 5-phenyl-2,3,4,5-tetrazolylthio group, 2-benzothiazolylthio group, 2-dodecylthio-5-thiophenyl Thio group, 2-phenyl-3-dodecyl-1,2,
4-triazolyl-5-thio group).

In the couplers of general formula (III) and (VI), R
¹² and R ¹³ may combine to form a 5- or 7-membered ring.

When R ¹¹ , R ¹² , R ¹³ or X is a divalent group to form a bis form, preferably R ¹¹ , R ¹² and R ¹³ are substituted or unsubstituted alkylene groups (eg methylene group, ethylene group, 1,10-decylene _group, -CH ₂ CH ₂ -O-C
H ₂ CH ₂ — and the like), a substituted or unsubstituted phenylene group (eg, 1,4-phenylene group, 1,3-phenylene group, Etc.), a —NHCO—R ¹⁴ —CONH— group (R ¹⁴ represents a substituted or unsubstituted alkylene group or phenylene group, for example, —NHCOCH ₂ CH ₂ CONH—, -S-R ¹⁴ -S- group (R ¹⁴ represents a substituted or unsubstituted alkylene group, _{e.g., -S-CH 2 CH 2 -S} , Etc., and X represents a divalent group at an appropriate place from the above monovalent group.

Formulas (III), (IV), (V), (VI), (VII),
The linking group represented by R ¹¹ , R ¹² , R ¹³ or X when the vinyl monomer contains those represented by (VIII) and (IX) is an alkylene group (a substituted or unsubstituted alkylene group, For example, methylene group, ethylene group, 1,
10 _{decylene, -CH 2 CH 2 OCH 2 CH} 2 -
Etc.), phenylene group (substituted or unsubstituted phenylene group, for example, 1,4-phenylene group, 1,3-phenylene group, Etc.), —NHCO—, CONH—, —O—, —OCO— and aralkylene groups (eg, Etc.) are included in combination with those selected from the above.

The following are preferred linking groups.

_{-NHCO -, - CH 2 CH 2} -, -CH ₂ CH ₂ NHCO-, _{-CONH-CH 2 CH 2 NHCO-,} -CH 2 CH 2 O-CH 2 CH 2 -NHCO-, The vinyl group has the general formulas (II), (III), (IV),
Substituents other than those represented by (V), (VI), (VII) or (VIII) may be taken, and preferable substituents are hydrogen atom, chlorine atom or lower alkyl group having 1 to 4 carbon atoms (eg methyl). Group, ethyl group).

Formulas (III), (IV), (V), (VI), (VII),
Monomers including those represented by (VIII) and (IX) may form copolymers with non-color forming ethylenic monomers that do not couple with the oxidation products of aromatic primary amine developers.

Acrylic acid, α is used as the non-color-forming ethylene-like monomer that does not couple with the oxidation product of the aromatic primary amine developing agent.
-Chloroacrylic acid, α-alkylacrylic acid (eg methacrylic acid) and esters or amides derived from these acrylic acids (eg acrylamide, n-butylacrylamide, t-butylacrylamide, diacetoneacrylamide, methacrylamide, Methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-
Ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxymethacrylate), methylenedibisacrylamide, vinyl esters (for example vinyl acetate, vinyl propionate and vinyl laurate),
Acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (eg vinyl ethyl ether). ), Maleic acid, maleic anhydride, maleic acid ester, N-vinyl-2-pyrrolidone, N-vinylpyridine and 2- and 4-vinylpyridine. Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can be used together. For example, n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate and diacetone acrylamide, and the like.

As is well known in the art of polymer color couplers, non-chromogenic ethylenically unsaturated monomers for copolymerization with solid water-insoluble monomer couplers are the physical and / or chemical properties of the copolymer formed, such as solubility. , The compatibility of the photographic colloid composition with the binder such as gelatin, its flexibility, thermal stability, etc. can be selected to be favorably influenced.

The polymer coupler used in the present invention may be water-soluble or water-insoluble, and among them, the polymer coupler latex is particularly preferable.

Specific examples of the pyrazoloazole-based magenta couplers represented by the general formula (II) used in the present invention and their synthesis methods are described in Japanese Patent Application Nos. 58-23434 and 58-151354.
58-45512, 59-27745, 58-1
42801, U.S. Pat. No. 3,061,432, and the like.

Specific examples of typical magenta couplers and vinyl monomers thereof according to the present invention are shown below, but the present invention is not limited thereto.

(M-1) (M-2) (M-3) (M-4) (M-5) (M-6) (M-7) (M-8) (M-9) (M-10) (M-11) (M-12) (M-13) (M-14) (M-15) (M-16) (M-17) (M-18) (M-19) (M-20) (M-21) (M-22) (M-23) (M-24) (M-25) (M-26) (M-27) (M-28) (M-29) (M-30) (M-31) (M-32) (M-33) (M-34) (M-35) (M-36) (M-37) (M-38) (M-39) (M-40) (M-41) (M-42) (M-43) (M-44) (M-45) (M-46) (M-47) (M-48) (M-49) (M-50) (M-51) (M-52) (M-53) (M-54) (M-55) (M-56) (M-57) (M-58) (M-59) (M-60) (M-61) (M-62) (M-63) (M-64) (M-65) (M-66) (M-67) (M-68) (M-69) (M-70) (M-71) (M-72) (M-73) (M-74) (M-75) (M-76) (M-77) (M-78) (M-79) (M-80) (M-81) (M-82) (M-83) Specific examples of the high boiling point organic solvent suitable for dissolving the magenta coupler used in the light-sensitive material of the present invention include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, etc.), Esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di- 2-ethylhexylphenylphosphonate, etc., benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxy) Benzoate), amides (diethyldodecane amide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (dioctyl) Azelates, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc., aniline derivatives (N, N-dibutyl-2-butoxy-5-)
tert-octylaniline) and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformaldehyde.

Various color couplers can be used in combination with the light-sensitive material of the present invention. Here, the color coupler means a compound capable of forming a dye by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. Useful color couplers are cyan, magenta and yellow color couplers, typical examples of which are naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds and open or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are Research Disclosure (RD) 17643 (December 1978) VII.
-D and patents cited in 18717 (November 1979).

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. A two-equivalent color coupler in which a coupling active position is replaced by a leaving group is more effective than a four-equivalent color coupler in which a hydrogen atom is present, because the coated silver amount can be reduced and high sensitivity can be obtained. It is also possible to use a coupler in which the color-forming dye has an appropriate diffusibility, a non-color-forming coupler, or a DIR coupler which releases a development inhibitor upon coupling reaction or a coupler which releases a development accelerator.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler. A specific example is US Pat. No. 2,40.
No. 7,210, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a two-equivalent yellow coupler, and US Pat. Nos. 3,408,194 and 3,447,928 are preferred.
No. 3,933,501 and No. 4,022.
No. 620 and other yellow couplers of oxygen atom elimination type or Japanese Patent Publication No. 58-10739, U.S. Pat. Nos. 4,401,752, 4,326,024, R
D18053 (April 1979), British Patent No. 1,42
No. 5,020, West German Application Publication No. 2,219,917,
Typical examples thereof include nitrogen atom releasing yellow couplers described in Nos. 2,261,361, 2,329,587 and 2,433,812. The α-pivaloyl acetanilide type coupler is excellent in the fastness of the color forming dye, especially the light fastness, while
The benzoylacetanilide coupler provides high color density.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the light-sensitive silver halide, preferably 0.01 to 0.5 mol for the yellow coupler and 0.003 for the magenta coupler. In the cyan coupler, it is 0.002 to 0.3 mol. The standard coating amount of the color coupler in the color paper is ^{4 to} 14 × 10 ⁻⁴ , 2 to ⁴ for each of the yellow, magenta and cyan couplers.
The range is 8 × 10 ⁻⁴ and 2 to 9 × 10 ⁻⁴ mol / m ² .
In the process of grain formation or physical ripening of the silver halide used in the present invention, it is possible to use cadmium salt, zinc salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or its complex salt, etc. In particular, it is preferable to use an iridium salt. The silver halide emulsion used in the present invention may be a so-called unripened emulsion which is not chemically sensitized, but it is usually chemically sensitized. A conventionally known method can be applied as the chemical sensitization method.

That is, a sulfur sensitizing method using a compound containing sulfur capable of reacting with active gelatin or silver (for example, thiosulfate, thiourea, mercapto compound, rhodanine), a reducing substance (for example, primary tin salt, amines, Reduction sensitization using hydrazine derivatives, formamidinesulfinic acid, silane compounds, noble metal compounds (eg, gold compounds, platinum)
A noble metal sensitization method using a periodic group VIII metal complex salt such as iridium or palladium) can be performed alone or in combination.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. That is, azoles {eg benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles, aminotriazoles, etc.); mercapto compounds {eg mercapto Thiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines, etc .; for example, thioketo such as oxadrinethione Compounds; azaindenes {eg triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes) ), Pentaazaindenes such like}; benzenethiosulfonate benzenesulfinate, known as antifoggants or stabilizers such as benzenesulfonic acid amide, can be added to many compounds.

For more detailed specific examples of these and methods of using them, see, for example, US Pat. Nos. 3,954,474 and 3,98.
Nos. 2,947 and 52-28660 can be used.

Further, a spectral sensitizer, a supersensitizer, a light absorber, a filter dye, a light reflector, a hardener, which can be used in the silver halide emulsion and other hydrophilic colloid layers used in the present invention,
Additives such as plasticizers, lubricants, coating aids (surfactants) antistatic agents, materials such as protective colloids (binders), supports that can be used in the color photographic light-sensitive material of the present invention, and treatments that can be used. For the method, see Research Disclosure N
22-29 of 17643 (December 1978) and 647-65 of the same magazine No.18716 (November 1979).
Those described on page 1 can be applied.

The color antifoggant, antifading agent, deterioration inhibitor against light, heat and humidity, and ultraviolet absorber, which are used in the light-sensitive material of the present invention and are suitable for magenta dye images, are described below.

For specific examples of antifoggants or stabilizers and their use, see, eg, US Pat. No. 3,954,474.
No. 3,982,947, Japanese Patent Publication No. 52-28660
Issue, Research Disclosure 17643 (197)
December 8th) VIA-VIM and EJ Bar "Stabilization of Photographic Silver Halide Emulsions" (Focal Press),
(Published in 1974).

A hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, a sulfonamidephenol derivative and the like may be contained as a color antifoggant or antifading agent.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Hydroquinones as organic anti-fading agents,
6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols,
Hindered phenols, mainly bisphenols,
Typical examples are gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl groups of these compounds. Further, (bissalicylaldoximato) nickel complex and (bis-N, N-dialkylthiocarbamate)
A metal complex represented by a nickel complex can also be used.

Specific examples of organic anti-fading agents are described in the specifications of the following patents.

Hydroquinones are described in US Pat. No. 2,360,290,
No. 2,418,613, No. 2,700,453
No. 2,701,197, No. 2,728,65
No. 9, No. 2,732,300, No. 2,735,7
No. 65, No. 3,982,944, No. 4,430,
No. 425, British Patent No. 1,363,921, US Pat. Nos. 2,710,801, 2,816,028, etc., 6-hydroxychromans, 5-hydroxycoumarans, spirochromans are U.S. Pat. No. 3,432,3
No. 00, No. 3,573,050, No. 3,574,
No. 627, No. 3,698,909, No. 3,76
4,337, JP-A-52-152225, and spiroindanes are described in U.S. Pat. No. 4,360,589,
p-Alkoxyphenols are described in US Pat. No. 2,735,
765, British Patent 2,066,975, JP-A-5
No. 9-10539, Japanese Patent Publication No. 57-19764, etc.
Hindered phenols are described in US Pat. No. 3,700,45
5, JP-A-52-72225, U.S. Pat. No. 4,22.
No. 8,235 and Japanese Patent Publication No. 52-6623, gallic acid derivatives, methylenedioxybenzenes, and aminophenols are described in U.S. Pat. Nos. 3,457,079, 4,332,886, and Japanese Patent Publication No. 56-21144, hindered amines are described in U.S. Pat. No. 3,336,1.
35, 4,268,593, British Patents 1,3
No. 26,889, No. 1,354,313, No. 1,
No. 410,846, Japanese Examined Patent Publication No. 51-1420, JP-A-5
8-114036, 59-53846, 59-
78344 and the like, ether of phenolic hydroxyl group,
Ester derivatives include U.S. Pat. Nos. 4,155,765, 4,174,220, 4,254,216,
No. 4,264,720, JP-A-54-145530.
No. 55-6321, No. 58-105147, No. 59-10539, Japanese Patent Publication No. 57-37856, U.S. Pat. No. 4,279,990, and Japanese Patent Publication No. 53-3263. Patent No. 4,050,938,
U.S. Pat. No. 4,241,155, British Patent No. 2,027,7
31 (A) and the like.

In order to prevent the deterioration of the magenta dye image, especially the deterioration by light, the spiroindanes described in JP-A-56-159644 and the hydroquinone diether or monoether described in JP-A-55-89835 are substituted. Chromans give favorable results. These compounds can achieve the object by usually coemulsifying 5 to 100% by weight of the corresponding color coupler with the coupler and adding them to the photosensitive layer. In order to prevent deterioration of the yellow dye image due to heat, humidity and light, a compound having both partial structures of hindered amine and hindered phenol in the same molecule as described in US Pat. No. 4,268,593 is preferable. Give a result. In order to prevent deterioration of the cyan dye image due to heat and especially light,
It is effective to introduce an ultraviolet absorber into both layers adjacent to the cyan color developing layer.

In the light-sensitive material of the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer. For example, benzotriazoles substituted with an aryl group described in U.S. Pat. Nos. 3,553,794, 4,236,013, Japanese Patent Publication No. 51-6540 and European Patent No. 57,160; Butadiene described in US Pat. Nos. 4,450,229 and 4,195,999, US Pat. Nos. 3,705,805 and 3,707,3
Cinnamic acid esters described in U.S. Pat.
215,530 and British Patent No. 1,321,355.
Benzophenones described in U.S. Pat.
Polymer compounds having an ultraviolet absorbing residue as described in Nos. 1,272 and 4,431,726 can be used. The UV-absorbing optical brighteners described in US Pat. Nos. 3,499,762 and 3,700,455 may be used. Typical examples of the ultraviolet absorber are described in Research Disclosure 24239 (June 1984) and the like.

The photographic emulsion used in the present invention is described in "Graph Kid Chemistry and Physique Photog" by Graphide.
raphique) (Paul Montel, 1967), Duffin "Photoemulsion Chemistry" (GFDuffin, Photographic Em
ulsion Chemistry) (Focal Press, 1966), Zelikmann et al., "Manufacturing and Coating of Photographic Emulsions" (VL
Zelikman et al, Making and Coating Photographic Emu
lsion) (Focal Press, Inc., 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, a combination thereof or the like. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. Among these methods, a normal crystal silver halide emulsion can be relatively easily obtained by using an emulsion preparation method which mainly uses a simultaneous mixing method or a controlled double jet method.

Further, an emulsion prepared by a so-called conversion method, which includes a step of exchanging silver halide already formed between the silver halide grain formation process and chemical sensitization with silver halide having a smaller solubility product, An emulsion which has undergone the same halogen exchange after the completion of the silver halide grain formation process can also be used.

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt may coexist.

The silver halide emulsion is usually used for coating after physical ripening, desilvering and chemical ripening after grain formation.

Known silver halide solvents (e.g., ammonia, Rhodan potassium or U.S. Pat. No. 3,271,157;
No. 1-12360, JP-A No. 53-82408, JP-A No. 53-144319, JP-A No. 54-100717 or JP-A No. 54-155828. It can be used in aging and chemical aging. To remove the soluble silver salt from the emulsion after physical ripening, noodle washing, flocculation sedimentation method, ultrafiltration method or the like is used.

The silver halide emulsion used in the present invention is a compound containing sulfur capable of reacting with active gelatin or silver (for example, thiosulfate,
Sulfur sensitization method using thioureas, mercapto compounds, rhodanins); Reduction sensitization method using reducing substances (eg, primary tin salts, amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds); metals Compounds (eg, gold complex salts, Pt, Ir, Pd, Rh, F
A noble metal sensitization method using a complex salt of Group VIII of the periodic table such as e) can be used alone or in combination.

Of the above chemical sensitizations, sulfur sensitization alone is more preferable.

In order to satisfy the target gradation of the color photographic light-sensitive material of the present invention, two or more kinds of monodisperse silver halide emulsions (monodispersity having different grain sizes in emulsion layers having substantially the same color sensitivity) are used. It is preferable that the material having the above-mentioned variation rate is mixed in the same layer or multi-layered in different layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used.

(Effects of the Invention) The processing method of the silver halide color photographic light-sensitive material of the present invention is excellent in color reproducibility and color image fastness, and the processing fluctuation, that is, the processing liquid composition, processing time, processing temperature, etc. It has the excellent property of small variation in tone.

That is, in the processing method of the silver halide color photographic light-sensitive material of the present invention, excellent development processing characteristics are exhibited, and the sensitivity with the passage of color development time when processing with a developing solution containing an aromatic primary amine as a main component The gradation change and the sensitivity change of the tomometry curve are significantly smaller in the color image forming method of the present invention than in the conventional method. Therefore, if the photosensitive material of the other layers (blue photosensitive yellow color forming layer, red photosensitive cyan color forming layer) of the photosensitive material has the same development processing time dependency, stabilization of development processing during continuous processing and reduction of processing time are possible. Is possible. Therefore, the image forming method using the silver halide color photographic light-sensitive material of the present invention has excellent suitability for rapid processing.

(Example) Next, the present invention will be described in more detail based on examples.

In the following description, the average particle size, the coefficient of variation, and the twin crystal content are the results of examining 277 or more particles using an electron micrograph.

Example 1 The silver halide grains (normal crystal emulsion A, non-normal crystal emulsion B), coupler α, coupler β, and coupler used in this example are as follows.

(1) Silver halide grains Normal crystal emulsion A According to the double jet mixing method, an aqueous solution of silver nitrate and an aqueous solution of alkali halide were added to and mixed with an aqueous solution of gelatin containing alkali halide to give an average grain size of 0.61 μm and a coefficient of variation of grain size. A cubic normal crystal emulsion of AgBr _0.7 Cl _0.3 containing 10% and a twin content of 0% was prepared. However, in the emulsion preparation, N, N'-dimethylethylenethiourea was used in order to increase the solubility of silver halide. It was then decanted and sulfur sensitized with thiourea. This is designated as Normal Crystal Emulsion A.

Unusual Crystal Emulsion B According to the double jet mixing method, an ammoniacal silver nitrate aqueous solution and an alkali halide aqueous solution are added and mixed with a gelatin aqueous solution containing an alkali halide to obtain an AgBr _0.67 having an average grain size of 0.48 μm and a grain size variation coefficient of 26%. An abnormal emulsion of Cl _0.33 was prepared. It was then decanted and sulfur sensitized with thiourea. This is designated as abnormal emulsion E.

(2) Coupler Coupler α Coupler β coupler Trioctyl phosphate 6.7 to coupler α 7.4g
m and 25 m of ethyl acetate were added and dissolved by heating. This solution was added to 100 m of an aqueous solution containing 10 g of gelatin and 1.0 g of sodium dodecylbenzenesulfonate, and the above coupler solution was finely emulsified and dispersed by a mechanical method. The total amount of this emulsified dispersion was normal crystal emulsion A99.
In addition to 0 g (containing 6.5 g of Ag), 2 as a hardener
% 1-Hydroxy-3,5-dichloro-S-triazine sodium 10 m was added, and the silver coating amount was 200 mg /
A sample was prepared by coating on a triacetate cellulose support so as to have m ² , and providing a gelatin layer on the coating layer. This is designated as sample S ₁ .

Samples S ₂ , S ₃ , S ₄ , S ₅ , and S ₆ were prepared by combining emulsions A and B with couplers α and β in the same manner.
It was created. The combination of coupler and emulsion, the amount of each component used and the amount of trioctyl phosphate of this sample are shown in Table 1.

Next, the samples S _{1 to} S ₆ were exposed and developed as follows.

(1) Development test Samples S _{1 to} S ₆ were tested at 1000C. M. S. Was exposed to light and treated with the following processing solutions.

Developer Benzyl alcohol 15 m Diethylenetriamine pentaacetic acid 5 g KBr 0.4 g Na ₂ SO ₃ 5 g Na ₂ CO ₃ 30 g Hydroxyamine sulphate 2 g 4-Amino-3-methyl-N-β- (methanesulfonamide) Ethylaniline ・ 3 / 2H ₂ SO ₄・ H ₂ O 4.5 g pH 10.1 to make water 1000 m pH Bleach fixer Ammonium thiosulfate (70 wt%) 150 m Na ₂ SO ₃ 5 g Na [Fe (EDTA)] 40 g EDTA 4 g Water PH 6.8 treatment step Temperature time Developer 33 ° C. 3 minutes 30 seconds Bleaching fixer 33 ° C. 1 minute 30 seconds Water washing 28-35 ° C. 3 minutes The photographic characteristics of each sample thus obtained were measured.

The results are shown in FIG. 1 and Table 2.

FIG. 1 shows that each sample has a sensitometry curve of 3 minutes and 30 seconds, and the center of the curve is 7:00 minutes (curve indicated by a chain double-dashed line) and 1 minute 30 seconds (a chain line indicated by a one-dot chain line). Curve) Optical density D = 1.5, D = 1.
0, the difference in sensitivity at D = 0.5 (logE (C.M.
S. )) Is shown.

Table 2 shows the optical density D of each sample corresponding to FIG.
= 0.5, 1.0, 1.5 and 1 minute 30 seconds, 3 minutes 30
The difference in sensitivity in the developing process for 7 seconds and 7 minutes 00 seconds is shown numerically.

From the results shown in FIGS. 1 and 2, it is seen that the combination of the coupler γ (pyrazolotriazole coupler) and the normal crystal emulsion A has the smallest sensitivity change of the sensitometry curve and the gradation change. It is found to give a small silver halide light-sensitive material.

(2) Development test After exposure in the same manner as in the samples S _{1 to} S ₆ development test, each sample was continuously processed in the following processing steps using Fuji Color Roll Processor FPRP-115 (manufactured by Fuji Photo Film Co., Ltd.).

[Processing method] The washing step was a three-step countercurrent washing from washing to washing.

In addition, the amount of the processing liquid carried in from the previous tank of each tank from the bleach-fixing step to washing with water is 60 m / m ² .

The conditions of color development process are all constant, and the replenishment amount is 1 m ^{2 of the} light-sensitive material.
At 161 m, the liquid used has the following formulation.

[Treatment liquid composition] The conditions of the bleach-fixing process are all constant, and the replenishing amount is 60 m / m ^{2 of the} light-sensitive material. The liquid used has the following formulation.

The conditions of the washing process are all constant, and the replenishing amount is 250 m per 1 m ^{2 of the} light-sensitive material. The liquid used has the following formulation.

1-Hydroxyethylidene-1,1-diphosphonic acid (60%) 2.0 m Aluminum sulfate 1.0 g Sulfanilamide 0.1 g Water was added to adjust the pH to 1 with ammonia water. The results of sensitometry when each sample was treated by 400 m ² are shown in FIG. 2 and Table 3. FIG. 2 shows the fluctuation of the sensitometry curve obtained by using the treatment liquid after the treatment of 400 m ² centered on the sensitometry curve obtained by using the treatment liquid immediately after the preparation in each sample. Is shown.

Corresponding to FIG. 2, Table 3 numerically represents the sensitivity differences at the optical densities D = 0.5, 1.0, and 1.5 for each sample.

According to Fig. 2 and Table 3, after the preparation, 400m ^{2 of} each sample
Sample 5, that is, coupler γ
It can be seen that the combination of the (pyrazoloazole coupler) and the normal crystal emulsion A gives the silver halide light-sensitive material in which the sensitivity change of the sensitometry curve is the smallest and the gradation change is the smallest.

Example 2 In this example, the effect of the coefficient of variation of grain size of silver halide emulsion grains was tested. Three kinds of normal crystal emulsions having different average particle sizes prepared in the same manner as the normal crystal emulsion A of Example 1 were mixed to obtain an average particle size of 0.61 μm.
m, particle size variation coefficient of 22% AgBr _0.7 C
A cubic normal crystal emulsion A'having a value of _0.3 and a twin content of 0% was prepared. This emulsion A ′ was combined with couplers α, β and γ to obtain samples S ₇ , S ₈ and S ₉ as shown in Table 4.

This sample was exposed and processed by the same method and conditions as in the development test of Example 1.

3 and 5 show the results of this sensitometry, and show the photographic characteristics of Samples S ₇ , S ₈ and S ₉ in correspondence with FIGS. 1 and 2 in the development test of Example 1. There is.

Comparing FIG. 3 and FIG. 1 and Tables 5 and 2, respectively, a normal monodisperse emulsion A having a high monodispersity (a variation coefficient of the size of silver halide grains of 10%) and a coupler γ, and a sample S were used. _{No. 5} is a combination of a normal crystal emulsion A ′ having a lower monodispersity (variation coefficient of the size of silver halide grains: 22%) and a coupler γ, and the sensitivity change of the sensitometry curve is smaller than that of Sample S ₉ , and It can be seen that a silver halide light-sensitive material having a small change in gradation can be provided. Further, it can be seen that the gradation of S ₉ is smaller than that of the sample S ₆ of the combination of the abnormal emulsion B and the coupler γ.

Next, samples S ₇ , S ₈ , and S ₉ were exposed and processed in the same manner as in Example 1, and S ₇ when the sensitometry curve obtained using the processing solution immediately after preparation was used as the center, S ₈ ,
The variation of the sensitometric curve when S ₉ was treated with 400 m ² was examined. The results are shown in FIGS. 4 and 6 corresponding to the development test of FIG. 2 and Table 3 of Example 1.

Comparing FIGS. 4 and 2 and Tables 6 and 3, respectively, when each sample was treated with 400 m ² after the preparation, normal crystal emulsion A (size of silver halide grains having high monodispersity) was obtained. than combined sample S ₉ towards the sample S ₅ combinations of coefficient of variation 10%) with the coupler γ is a coupler γ monodispersity less regular crystal emulsions a '(coefficient of variation 22% of the size of the silver halide grains) It can be seen that a silver halide light-sensitive material having a small sensitometric curve sensitivity change and a small gradation change can be provided. Further, it can be seen that the sample S ₉ has a smaller change in gradation than the sample S _{6 in} which the abnormal emulsion B and the coupler γ are combined.

Example 3 In the same manner as in Example 1, the coupler (M-75),
Creating the samples S ₁₀ to S ₁₃ in combination Emulsion A or B with respect to (M-81). Table 7 shows the combination of coupler and emulsion, the amount of each component used and the amount of trioctyl phosphate in these samples.

The following samples S _{11 to} S ₁₃ were exposed in the same manner as in the development test (2) of Example 1 and then subjected to continuous development processing.

Table 8 shows the results of sensitometry when each sample was treated by 400 m ² .

Table 8 shows the optical density D = 0.5, 1.
The difference in sensitivity at 0 and 1.5 is numerically represented.

The effect of the present invention is clear from Table 8. Pyrazoloazole couplers (M-75) and (M-
81), the sensitivity change of the sensitometry curve is small due to the combination with normal crystal emulsion A,
Moreover, a silver halide color photographic light-sensitive material having a small gradation change can be obtained.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between development processing time and sensitometry of silver halide color photographic light-sensitive materials, and FIG. 2 shows the relationship between fluctuations in processing solutions of silver halide color photographic light-sensitive materials and sensitometry. Graph, FIG. 3 is a graph showing the relationship between development processing time and sensitometry of silver halide color photographic light-sensitive material, and FIG. 4 is a relationship between fluctuation of processing solution of silver halide color photographic light-sensitive material and sensitometry. It is a graph which shows.

Claims (1)

[Claims] 1. A pyrazoloazole-based coupler represented by the following general formula (VI) or (VII) and the following formula: AgCl _x Br _y I _1-xy (wherein 0 <x ≦ 1, 0 ≦ y <10 ≦ 1-x−y ≦ 0.02), having a silver halide grain consisting of cubic normal crystals having a twin content of 5% or less and having a coefficient of variation of 0.20 or less. (However, the emulsion is substantially {11
A crystal plane having a ridge in the center of the 0} plane and / or {1
A silver halide color photographic light-sensitive material having a 10} face and having a silver halide composition substantially free of silver halide grains consisting of silver bromide and / or silver iodobromide) A method for forming a color image, which comprises performing continuous color development processing while replenishing a developing solution. (In the formula, R ¹¹ and R ¹² may be the same or different from each other, and each is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, Acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino Group, an aryloxycarbonylamino group, a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and X is a hydrogen atom or an aromatic primary amine developing agent. Drug oxidant The coupling reaction represents a group capable of being released.)